The invention relates to a composition for the oxidation dyeing of keratinous fibers, and in particular of human keratinous fibers such as human hair, comprising at least one pyrazoloazole compound as an oxidation base, the method of dyeing which employs this composition, and novel pyrazoloazoles.
It is well known to dye keratinous fibers, and in particular human hair, using dyeing compositions comprising oxidation dye precursors, such as ortho- or para-phenylenediamines, ortho- or para-aminophenols, and heterocyclic compounds, which are generally referred to as oxidation bases. The oxidation dye precursors, or oxidation bases, are colorless or lightly colored compounds which, when combined with oxidizing products, can give rise, by an oxidative coupling process, to colored and coloring compounds.
It is also known that the shades obtained with these oxidation bases can be varied by combining them with couplers or coloring modifiers, the latter being chosen in particular from aromatic meta-diamines, meta-aminophenols, meta-diphenols and certain heterocyclic compounds, such as indole compounds.
The diversity of the molecules employed as oxidation bases and couplers makes it possible to obtain a wide range of colors.
The xe2x80x9cpermanentxe2x80x9d coloration obtained by these oxidation dyes should optimally meet certain conditions. Thus, it should have no toxicological effects, should allow shades of the desired intensity to be obtained, and should have good resistance to external agents (light, bad weather, washing, permanent waving, perspiration or rubbing).
The dyes should also allow white hairs to be covered and, finally, they should be as unselective as possible, that is to say, they should allow the smallest possible differences in coloration to be produced over the entire length of a single keratinous fibre, which may vary in condition of sensitization or damage from its tip to its root. They should also exhibit good chemical stability in the formulations and a good toxicological profile.
The inventors have discovered that it is possible to obtain powerful novel dyes which are not very selective, are particularly resistant to various external agents which keratinous fibers can be subjected to, and which are capable of generating intense colorings in varied shades by using, as oxidation base, pyrazoloazole compounds of formula (I) defined below.
This discovery is the basis of the present invention.
The first aspect of the invention is thus a composition for the oxidation dyeing of keratinous fibers, and in particular human keratinous fibers such as hair, comprising, in a medium suitable for dyeing:
as oxidation base, at least one pyrazoloazole compound of formula (I) or at least one acid addition salt thereof: 
in which:
R1 represents: a hydrogen atom; a linear or branched C1-C20 alkyl radical, optionally substituted by 1 or 2 radicals R chosen from a halogen atom, a nitro radical, a cyano radical, a hydroxyl radical, an alkoxy radical, an aryloxy radical, an amino radical, an alkylamino radical, an acylamino radical, a carbamoyl radical, a sulphonamido radical, a sulphamoyl radical, an imido radical, an alkylthio radical, an arylthio radical, an aryl radical, such as phenyl or naphthyl, a (C1-C4)alkoxy-carbonyl radical and an acyl radical; an aryl radical (such as phenyl or naphthyl), optionally substituted by 1 or 2 radicals R as defined above; a 5- or 6-membered heterocycle containing at least one nitrogen, oxygen or sulphur atom (such as pyridyl, quinolyl, pyrrolyl, morpholyl, furanyl, tetrahydrofuranyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl, imidazolyl or thiadiazolyl), wherein said heterocycle is optionally substituted by 1 or 2 radicals R as defined above;
when R1 denotes a C1-C4 alkyl radical, an aryl radical or a 5- or 6-membered heterocycle (as defined above), it can be connected to the carbon atom of the pyrazole via an oxygen, nitrogen or sulphur atom (in this case, R1 becomes XR1 with X=O, NH or S);
R1 can, additionally, denote a halogen atom (such as bromine, chlorine or fluorine); an acyl radical; a sulphonyl radical; a sulphinyl radical; a phosphonyl radical; a carbamoyl radical; a sulphamoyl radical; a cyano radical; a siloxy radical; an amino radical; an acylamino radical; an acyloxy radical; a carbamoyloxy radical; a sulphonamide radical; an imide radical; a ureido radical; a sulphamoylamino radical; a (C1-C4)alkoxy-carbonylamino radical; an aryloxycarbonylamino radical; a (C1-C4)alkoxy-carbonyl radical; an aryloxycarbonyl radical; a carboxyl radical; or a hydroxyl radical; R2 denotes a hydrogen atom; a C1-C4 alkyl radical; a C1-C4 monohydroxyalkyl radical; a C2-C4 polyhydroxyalkyl radical; a C1-C4 aminoalkyl radical; a (CH2)pxe2x80x94Xxe2x80x94 (CH2)qORxe2x80x2 radical in which p and q are identical or different integers ranging from 1 to 3, Rxe2x80x2 represents a hydrogen atom or a methyl radical, and X denotes an oxygen atom or an NRxe2x80x3 group in which Rxe2x80x3 represents a hydrogen atom or a methyl radical; a (C1-C4)alkoxy(C2-C4)alkyl radical; or a di(C1-C4)alkylamino(C1-C4)alkyl radical; and
Za, Zb, and Zc represent, independently of one another, a nitrogen atom or a carbon atom carrying an R3 or R4 radical, where R3 and R4 have the same meanings as those indicated above for the R1 radical, with the proviso that at least one of the Za, Zb, and Zc radicals is other than a carbon atom; R3 and R4 can also together form a substituted or unsubstituted aromatic ring, such as a phenyl ring.
Preferred R1 radicals of the compounds of formula (I) defined above are chosen from a hydrogen atom; a linear or branched C1-C4 alkyl radical; a phenyl ring; a phenyl ring substituted by a halogen atom, a C1-C4 alkyl radical, a C1-C4 alkoxy radical, a nitro radical, an amino radical, a trifluoromethyl radical or a C1-C4 alkylamino radical; a benzyl radical; a benzyl radical substituted by a halogen atom, a C1-C4 alkyl radical, a C1-C4 alkoxy radical, a nitro radical, an amino radical, a trifluoromethyl radical or a C1-C4 alkylamino radical; a heterocycle chosen from the thiophene, furan or pyridine rings; a trifluoromethyl radical; a (CH2)pxe2x80x94Xxe2x80x94(CH2)qxe2x80x94ORxe2x80x2 radical in which p and q are identical or different integers ranging from 1 to 3, where Rxe2x80x2 represents a hydrogen atom or a methyl radical and X denotes an oxygen atom or an NRxe2x80x3 radical in which Rxe2x80x3 denotes a hydrogen atom or a methyl radical; a C1-C4 hydroxyalkyl radical; a C1-C4 aminoalkyl radical; a C1-C4 alkylamino radical; a di(C1-C4)alkylamino radical; an arylamino radical; an alkoxy radical chosen from methoxy, ethoxy and phenoxy; a halogen atom chosen from bromine, chlorine and fluorine; a carboxyl group; a C1-C4 alkoxycarbonyl radical; a phenyloxycarbonyl radical; a methylthio radical; an ethylthio radical; a phenylthio radical; a methanesulphonyl radical; a cyano radical; an amino radical; or a hydroxyl radical.
More preferred R1 radicals of the compounds of formula (I) defined above are chosen from a hydrogen atom; an alkyl radical chosen from the methyl, ethyl, isopropyl and tert-butyl radicals; a halogen atom chosen from chlorine and fluorine; a phenyl radical; a toluyl radical; a 4-chlorophenyl radical; a 4-methoxyphenyl radical; a 3-methoxyphenyl radical; a 2-methoxyphenyl radical; a benzyl radical; a heterocycle chosen from the pyridyl, furyl and thienyl rings; a trifluoromethyl radical, a hydroxymethyl radical; an aminomethyl radical; a methoxy radical; an ethoxy radical; a methylamino radical; an ethylamino radical; a dimethylamino radical; a carboxyl radical; a methoxycarbonyl radical; an ethoxycarbonyl radical and a cyano radical.
More particularly preferred R1 radicals are chosen from: a hydrogen atom; a chlorine atom; a methyl radical; an ethyl radical; a phenyl radical; a toluyl radical; a 4-chlorophenyl radical; a 4-methoxyphenyl radical; a benzyl radical; a trifluoromethyl radical; a methoxy radical; an ethoxy radical; a carboxyl radical; a methylamino radical; a dimethylamino radical and a cyano radical. Preferred R2 radicals of the compounds of formula (I) defined above are chosen from a hydrogen atom; a methyl radical and a xcex2-hydroxyethyl radical.
More preferably, the R2 radical represents a hydrogen atom.
Preferred R3 and R4 radicals of the compounds of formula (I) defined above are chosen from a hydrogen atom; a hydroxyl radical; an amino radical; a linear or branched C1-C4 alkyl radical; a trifluoromethyl radical; a phenyl ring; a phenyl ring substituted by one or two radicals R chosen from a halogen atom, a C1-C4 alkyl radical, a C1-C4 alkoxy radical, a hydroxyl radical, a carboxyl radical, a nitro radical, a C1-C4 alkylthio radical, a methylenedioxy radical, an amino radical, a trifluoromethyl radical and a C1-C4 alkylamino radical; a benzyl radical; a benzyl radical substituted by a halogen atom, a methyl or isopropyl radical or a methoxy radical; a C1-C4 monohydroxyalkyl radical; a C1-C4 aminoalkyl radical; a (C1-C4)alkylamino(C1-C4)alkyl radical; an alkoxy radical chosen from the methoxy, ethoxy and phenoxy radicals; a methylthio radical; an ethylthio radical; a phenylthio radical; a methanesulphonyl radical; or a substituted or unsubstituted aromatic ring formed jointly by R3 and R4, such as a phenyl ring, pyridyl ring or phenyl ring substituted by a sulphonyl radical, a halogen atom, a C1-C4 alkoxy radical, a C1-C4 alkyl radical, a nitro radical, a cyano radical, an amino radical, a C1-C4 alkylamino radical or a trifluoromethyl radical.
More preferred R3 and R4 radicals of the compounds of formula (I) defined above are chosen from a hydrogen atom; an alkyl radical chosen from the methyl, ethyl, isopropyl, n-propyl and tert-butyl radicals; a phenyl ring; a toluyl ring; a 2-, 3- or 4-chlorophenyl ring; a 3- or 4-hydroxyphenyl ring; a 3- or 4-aminophenyl ring; a 3- or 4-methoxyphenyl ring; a 4-trifluoromethylphenyl ring; a benzyl ring; a trifluoromethyl radical; a hydroxymethyl radical; a hydroxyethyl radical; a hydroxyisopropyl radical; an aminomethyl or aminoethyl radical; a methoxy or ethoxy radical; a methylthio or ethylthio radical; or a substituted or unsubstituted aromatic ring formed jointly by R3 and R4, such as a phenyl, toluyl, sulphonylphenyl and chlorophenyl ring.
More particularly preferred R3 and R4 radicals are chosen from a hydrogen atom; a methyl radical; an ethyl radical; an isopropyl radical; a phenyl ring; a 4-chlorophenyl ring; a 4-methoxyphenyl ring; a 4-aminophenyl ring; a methoxy or ethoxy radical; a methylthio or ethylthio radical and a phenyl ring formed jointly by R3 and R4.
Preferred compounds of formula (I) in accordance with the invention, are:
i) the pyrazolo[1,5-b]-1,2,4-triazoles of formula (Ia) and the acid addition salts thereof: 
ii) the pyrazolo[3,2-c]-1,2,4-triazoles of formula (Ib) and the acid addition salts thereof: 
iii) the pyrazolotetrazoles of formula (Ic) the acid addition salts thereof: 
iv) the pyrazolo[1,5-a]imidazoles of formula (Id) and the acid addition salts: 
(v) the pyrzolo[5,1-e]pyrazoles of formula (Ie) and the acid addition salts: 
vi) the pyrazolo[5,1-e]-1,2,3-triazoles of formula (If) and the acid addition salts thereof: 
in which R1, R2, R3 and R4 have the same meanings as those indicated above for formula (I).
Preferred compounds of formulae (Ia) and (Ib), are those in which:
R1 denotes a hydrogen atom or a methyl, trifluoromethyl, carboxyl, phenyl, ethoxy, cyano, ethylthio, amino or hydroxyl radical;
R2 denotes a hydrogen atom;
R3 denotes a hydrogen atom or a methyl, xcex2-aminoethyl, ethyl, isopropyl, phenyl, xcex2-hydroxyethyl, methylthio or ethoxy radical.
Preferred compounds of formula (Ic), are those in which:
R1 denotes a hydrogen atom or a methyl, trifluoromethyl, carboxyl, phenyl, ethoxy or cyano radical;
R2 denotes a hydrogen atom.
Preferred compounds of formula (Id), are those in which:
R1 denotes a hydrogen atom or a methyl, trifluoromethyl, carboxyl, phenyl, ethoxy, cyano, amino, ethylthio or hydroxyl radical;
R2 denotes a hydrogen atom;
R3 and R4 respectively denote a hydrogen atom and a hydrogen atom, a hydrogen atom and a methyl radical, a methyl radical and a hydrogen atom, a hydrogen atom and a phenyl radical, or a hydroxyl radical and a hydrogen atom; or R3 and R4 jointly form a phenyl ring.
Preferred compounds of formula (Ie), are those in which:
R1 denotes a hydrogen atom or a methyl, trifluoromethyl, carboxyl, phenyl, ethoxy or cyano radical;
R2 denotes a hydrogen atom;
R3 and R4 respectively denote a hydrogen atom and a methyl radical, a methyl radical and a hydrogen atom, a methyl radical and a methyl radical, a hydrogen atom and a phenyl radical, or a hydrogen atom and an amino radical. Preferred compounds of formula (If), are those in which:
R1 denotes a hydrogen atom or a methyl, trifluoromethyl, carboxyl, phenyl, ethoxy or cyano radical;
R2 denotes a hydrogen atom;
R3 denotes a hydrogen atom or a methyl radical.
Preferred compounds of formulae (Ia) which can be used in the dyeing compositions, in accordance with the invention, are:
7-amino-2-methylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-2-phenylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-methyl-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-methyl-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-methyl-2-phenylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-carboxy-2-methylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-carboxy-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-carboxy-2-isopropylpyrazolo[1,5-b ]-1,2,4-triazole;
7-amino-6-carboxy-2-phenylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-phenyl-2-methylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-phenyl-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-phenyl-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;
6,7-diamino-2-methylpyrazolo[1,5-b]-1,2,4-triazole;
6,7-diamino-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;
6,7-diamino-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;
6,7-diamino-2-phenylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-ethylthio-2-methylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-ethylthio-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-ethylthio-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-ethylthio-2-phenylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-ethoxy-2-methylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-ethoxy-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-ethoxy-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-ethoxy-2-phenylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-methyl-2-(2xe2x80x2-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-carboxy-2-(2xe2x80x2-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-phenyl-2-(2xe2x80x2-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-ethylthio-2-(2xe2x80x2-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;
7-amino-2-(2xe2x80x2-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;
7-amino-2-(2xe2x80x2-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-methyl-2-(2xe2x80x2-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-ethylthio-2-(2xe2x80x2-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-carboxy-2-(2xe2x80x2-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-phenyl-2-(2xe2x80x2-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;
6,7-diamino-2-(2xe2x80x2-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;
6,7-diamino-2-(2xe2x80x2-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-ethoxy-2-(2xe2x80x2-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-ethoxy-2-(2xe2x80x2-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;
and the acid addition salts thereof.
Preferred compounds of formulae (Ib) which can be used in the dyeing compositions, in accordance with the invention, are:
7-amino-3-methylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-3-ethylpyrazolo[3,2-c]-1,2,4triazole;
7-amino-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-3-(2xe2x80x2-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-3-(2xe2x80x2-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-methyl-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-3,6-dimethylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-methyl-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-methyl-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-methyl-3-(2xe2x80x2-aminoethyl)pyrazolo[3,2-c]-1,2,4triazole;
7-amino-6-methyl-3-(2xe2x80x2-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-methyl-3-(methylthio)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-phenyl-3-methylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-phenyl-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-phenyl-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-phenyl-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-phenyl-3-(2xe2x80x2-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-phenyl-3-(2xe2x80x2-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-phenyl-3-(methylthio)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-ethylthio-3-methylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-ethylthio-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-ethylthio-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-ethylthio-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-ethylthio-3-(2xe2x80x2-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-ethylthio-3-(2xe2x80x2-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-trifluoromethyl-3-(methylthio)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-(trifluoromethyl)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-carboxy-3-methylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-carboxy-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-carboxy-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-carboxy-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-carboxy-3-(2xe2x80x2-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-carboxy-3-(2xe2x80x2-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;
6,7-diamino-3-methylpyrazolo[3,2-c]-1,2,4-triazole;
6,7-diamino-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;
6,7-diamino-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;
6,7-diamino-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-ethoxy-3-methylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-ethoxy-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-ethoxy-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-ethoxy-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-ethoxy-3-(2xe2x80x2-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-ethoxy-3-(2xe2x80x2-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;
6,7-diamino-3-(2xe2x80x2-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;
6,7-diamino-3-(2xe2x80x2-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;
and the acid addition salts thereof.
Preferred compounds of formulae (Ic) which can be used in the dyeing compositions, in accordance with the invention, are:
7-amino-6-methylpyrazolo[5,1-e]tetrazole;
7-amino-6-phenylpyrazolo[5,1-e]tetrazole;
7-amino-6-carboxypyrazolo[5,1-e]tetrazole;
and the acid addition salts thereof.
Preferred compounds of formulae (Id) which can be used in the dyeing compositions in accordance with the invention, are:
7-amino-2-methylpyrazolo[1,5-a]imidazole;
7-amino-2-phenylpyrazolo[1,5-a]imidazole;
7-aminopyrazolo[1,5-a]benzimidazole;
7-amino-6-methylpyrazolo[1,5-a]imidazole;
7-amino-2,6-dimethylpyrazolo[1,5-a]imidazole;
7-amino-6-methyl-2-phenylpyrazolo[1,5-a]imidazole;
7-amino-6-methylpyrazolo[1,5-a]benzimidazole;
7-amino-6-phenylpyrazolo[1,5-a]imidazole;
7-amino-6-phenyl-2-methylpyrazolo[1,5-a]imidazole;
7-amino-2,6-diphenylpyrazolo[1,5-a]imidazole;
7-amino-6-phenylpyrazolo[1,5-a]benzimidazole;
7-amino-6-carboxypyrazolo[1,5-a]imidazole;
7-amino-6-carboxy-2-methylpyrazolo[1,5-a]imidazole;
7-amino-6-carboxy-2-phenylpyrazolo[1,5-a]imidazole;
7-amino-6-carboxypyrazolo[1,5-a]benzimidazole;
7-amino-6-ethoxypyrazolo[1,5-a]imidazole;
7-amino-6-ethoxy-2-methylpyrazolo[1,5-a]imidazole;
7-amino-6-ethoxy-2-phenylpyrazolo[1,5-a]imidazole;
7-amino-6-ethoxypyrazolo[1,5-a]benzimidazole;
7-amino-6-(trifluoromethyl)pyrazolo[1,5-a]benzimidazole;
7-amino-6-aminopyrazolo[1,5-a]imidazole;
7-amino-6-amino-2-methylpyrazolo[1,5-a]imidazole;
7-amino-6-amino-2-phenylpyrazolo[1,5-a]imidazole;
7-amino-6-aminopyrazolo[1,5-a]benzimidazole;
7-amino-6-(ethylthio)pyrazolo[1,5-a]imidazole;
7-amino-6-ethylthio-2-methylpyrazolo[1,5-a]imidazole;
7-amino-6-ethylthio-2-phenylpyrazolo[1,5-a]imidazole;
7-amino-6-methyl-2-hydroxypyrazolo[1,5-a]imidazole;
7-amino-6-phenyl-2-hydroxypyrazolo[1,5-a]imidazole;
7-amino-6-ethoxy-2-hydroxypyrazolo[1,5-a]imidazole;
7-amino-6-ethylthio-2-hydroxypyrazolo[1,5-a]imidazole;
6,7-diamino-2-hydroxypyrazolo[1,5-a]imidazole;
and the acid addition salts thereof.
Preferred compounds of formulae (Ie) which can be used in the dyeing compositions in accordance with the invention, are:
5,8-diamino-4-methylpyrazolo[5,1-e]pyrazole;
5,7,8-triamino-4-methylpyrazolo[5,1-e]pyrazole;
and the acid addition salts thereof.
Preferred compounds of formulae (If) which can be used in the dyeing compositions in accordance with the invention, are:
6-amino-5-methylpyrazolo[5,1-e]-1,2,3-triazole;
6-amino-5-phenylpyrazolo[5,1-e]-1,2,3-triazole;
and the acid addition salts thereof.
The pyrazoloazole compound(s) formula (I) preferably represent(s) from 0.0005 to 12% by weight approximately relative to the total weight of the dyeing composition, and more preferably, from 0.005 to 6% by weight, approximately, of the total weight.
The medium (or vehicle) suitable for dyeing is, for example, water, a water/alcohol mixture, or a mixture of water and of at least one organic solvent to dissolve any compounds which are not be sufficiently water soluble. Preferred organic solvents are, for example, C1-C4 lower alkanols, such as ethanol and isopropanol; glycerol; glycols and glycol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and aromatic alcohols, such as benzyl alcohol or phenoxyethanol, and mixtures thereof.
The solvents can be present in proportions ranging from 1 to 40% by weight approximately relative to the total weight of the dyeing composition, and even more preferably from 5 to 30% by weight approximately.
The pH of the dyeing composition in accordance with the invention generally ranges from 3 to 12, approximately, and preferably approximately from 5 to 11. It can be adjusted to the desired value by means of acidifying or basifying agents commonly used in dyeing keratinous fibers, or alternatively using conventional buffer systems.
Preferred acidifying agents include, for example, inorganic and organic acids, such as hydrochloric acid, orthophosphoric acid, sulphuric acid, carboxylic acids, such as acetic acid, tartaric acid, citric acid or lactic acid, and sulphonic acids.
Preferred basifying agents include, for example, aqueous ammonia, alkaline carbonates, alkanolamines, such as mono-, di- and triethanolamines and derivatives thereof, sodium hydroxide, potassium hydroxide, and the compounds of following formula (II): 
in which W is a propylene residue optionally substituted by a hydroxyl radical or a C1-C4 alkyl radical; and R6, R7, R8 and R9, which are identical or different, represent a hydrogen atom, a C1-C4 alkyl radical or C1-C4 hydroxyalkyl radical.
In a preferred embodiment, the dyeing composition in accordance with the invention additionally includes at least one coupler in order to modify or enrich with highlights the shades obtained by employing the compounds of formula (I).
The couplers which can be used in the dyeing composition in accordance with the invention may be chosen from the couplers used conventionally in oxidation dyeing, among which generally preferred couplers are: meta-phenylenediamines, meta-aminophenols, meta-diphenols and heterocyclic couplers.
More particularly preferred couplers are chosen from 2-methyl-5-aminophenol, 5-N-(xcex2-hydroxyethyl)amino-2-methylphenol, 3-aminophenol, 1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene, 4-chloro-1,3-dihydroxy-benzene, 2,4-diamino-1-(xcex2-hydroxyethyloxy)benzene, 2-amino-4-(xcex2-hydroxyethyl)amino-1-methoxybenzene, 1,3-diaminobenzene, 1,3-bis(2,4-diaminophenoxy)-propane, sesamol, xcex1-naphthol, 6-hydroxyindole, 4-hydroxyindole, 4-hydroxy-N-methylindole, 6-hydroxyindoline, 2,6-dihydroxy-4-methylpyridine, 1H-3-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one, 2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole, 2,6-dimethyl[3,2-c]-1,2,4-triazole, 6-methylpyrazolo-[1,5-a]benzimidazole, and the acid addition salts thereof.
When present, the coupler(s) preferably represent(s) from 0.0001 to 10% by weight approximately relative to the total weight of the dyeing composition, and even more preferably from 0.005 to 5% by weight approximately relative to this weight.
The dyeing composition in accordance with the invention may additionally comprise, as well as the above-defined dyes, at least one additional oxidation base chosen from the oxidation bases which are conventionally employed in oxidation dyeing, among which preferred oxidation bases are: para-phenylenediamines, bisphenylalkylenediamines, para-aminophenols, ortho-aminophenols and heterocyclic bases which are different from the pyrazoloazole compounds of formula (I) used in accordance with the invention.
Among the para-phenylenediamines, preferred para-phenylenediamine are: para-phenylenediamines, para-toluylenediamine, 2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediameine, N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine, N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline, N,N-bis(xcex2-hydroxyethyl)-para-phenylenediamine, 4-N,N-bis(xcex2-hydroxyethyl)amino-2-methylaniline, 4-N,N-bis(xcex2-hydroxyethyl)amino-2-chloroaniline, 2-(xcex2-hydroxyethyl)-para-phenylenediamine, 2-fluoro-para-phenylenediamine, 2-isopropyl-para-phenylenediamine, N-(xcex2-hydroxypropyl)-para-phenylenediamine, 2-hydroxymethyl-para-phenylenediamine, N,N-dimethyl-3-methyl-para-phenylenediamine, N,N-(ethyl,xcex2-hydroxyethyl)-para-phenylenediamine, N-(xcex2,xcex3-dihydroxypropyl)-para-phenylenediamine, N-(4xe2x80x2-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamine, 2-(xcex2-hydroxyethyloxy)-para-phenylenediamine, 2-(xcex2-acetylaminoethyloxy)-para-phenylenediamine, N-(xcex2-methoxyethyl)-para-phenylenediamine, and the acid addition salts thereof.
Among the abovementioned para-phenylenediamines, more preferred para-phenylenediamines are: para-phenylenediamine, para-toluylenediamine, 2-isopropyl-para-phenylenediamine, para-phenylenediamine, 2-(xcex2-hydroxyethyl)-para-phenylenediamine, 2-(xcex2-hydroxyethyloxy)-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine, N,N-bis(xcex2-hydroxyethyl)-para-phenylenediamine, 2-chloro-para-phenylenediamine, 2-(xcex2-acetylaminoethyloxy)-para-phenylenediamine, and the acid addition salts thereof.
Among the bisphenylalkylenediamines, preferred bisphenylalkylenediamines are: N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)-1,3-diamino-2-propanol, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4xe2x80x2-aminophenyl)ethylenediamine, N,Nxe2x80x2-bis(4-aminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(xcex2-hydroxyethyl)-N,Nxe2x80x2-bis(4-aminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(4-methylaminophenyl)tetramethylenediamine, N,Nxe2x80x2-bis(ethyl)-N,Nxe2x80x2-bis(4xe2x80x2-amino-3xe2x80x2-methylphenyl)ethylenediamine, 1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and the acid addition salts thereof.
Among the para-aminophenols, preferred para-aminophenols are: para-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 4-amino-3-(hydroxymethyl)phenol, 4-amino-2-methylphenol, 4-amino-2-(hydroxymethyl)phenol, 4-amino-2-(methoxymethyl)phenol, 4-amino-2-(aminomethyl)phenol, 4-amino-2-[(xcex2-hydroxyethyl)-aminomethyl]phenol, 4-amino-2-fluorophenol, and the acid addition salts thereof.
Among the ortho-aminophenols, preferred ortho-aminophenols are: 2-aminophenol, 2-amino-5-methylphenol, 2-amino-6-methylphenol, 5-acetamido-2-aminophenol, and the acid addition salts thereof.
Among the heterocyclic bases, preferred heterocyclic bases are: pyridine derivatives, pyrimidine derivatives and pyrazole derivatives.
When used, the additional oxidation base(s) preferably represent(s) from 0.0005 to 12% by weight approximately relative to the total weight of the dyeing composition and, more preferably from 0.005 to 6% by weight approximately relative to this weight.
The acid addition salts used within the scope of the dyeing compositions of the invention (compounds of formula (I), additional oxidation bases and couplers) are chosen in particular from hydrochlorides, hydrobromides, sulphates, citrates, succinates, tartrates, tosylates, benzenesulphonates, lactates and acetates.
The dyeing composition in accordance with the invention can additionally contain one or more direct dyes which can be chosen from nitrated dyes of the benzene series.
The dyeing composition in accordance with the invention can also contain various adjuvants used conventionally used in hair dyeing compositions, such as anionic, cationic, non-ionic, amphoteric or zwitterionic surfactants or mixtures thereof, anionic, cationic, non-ionic, amphoteric or zwitterionic polymers or mixtures thereof, inorganic or organic thickeners, antioxidants, penetration agents, sequesterants, fragrances, buffers, dispersants, conditioners such as, for example, modified or non-modified, volatile or non-volatile silicones, film formers, ceramides, preservatives or opacifiers.
Of course, a person skilled in the art will take care to choose the optional additional compound(s) such that the advantageous properties intrinsically associated with the dyeing composition in accordance with the invention are not, or not substantially, adversely affected by the additions envisaged.
The dyeing composition according to the invention may be in various forms, such as in the form of liquids, creams or gels, or any other form which is suitable for dyeing keratinous fibers, and in particular human hair.
Another aspect of the invention is the use of the compounds of formula (I) as defined above as oxidation base in compositions for the oxidation dyeing of keratinous fibers, and in particular human keratinous fibers, such as hair.
The invention also provides a process for dyeing keratinous fibers, and in particular of human keratinous fibers such as hair using the dyeing composition as defined above.
According to this process, at least one dyeing composition as defined above is applied to the fibers for a period which is sufficient to develop the desired coloration, either in air or with the aid of an oxidizing agent.
According to one embodiment of the process of the invention, the dyeing of the fibers can be carried out without the addition of an oxidizing agent, solely by contact with the oxygen in the air. In this case, the dyeing composition can optionally include oxidation catalysts in order to accelerate the oxidation process.
A preferred oxidation catalyst is, for example, a metal salt, such as manganese, cobalt, copper, iron, silver and zinc. A more preferred oxidation catalyst is, for example, manganese diacetate tetrahydrate, manganese dichloride, manganese triacetate and its hydrates, manganese trichloride, zinc dichloride, zinc diacetate dihydrate, zinc carbonate, zinc dinitrate, zinc sulphate, iron dichloride, iron sulphate, iron diacetate, cobalt diacetate tetrahydrate, cobalt carbonate, cobalt dichloride, cobalt sulphate heptahydrate, cupric chloride or ammoniacal silver nitrate.
When used, the metal salt generally represent from 0.001 to 4% by weight of relative to the total weight of the dyeing composition, and more preferably from 0.005 to 2% by weight relative to the total weight of the dyeing composition.
According to another embodiment of the process of the invention, at least one dyeing composition as defined above is applied to the fibers, the color being developed at an acidic, neutral or alkaline pH with the aid of an oxidizing agent which is added right at the time when the dyeing composition is employed or which is present in an oxidizing composition which is applied separately from the dye composition at the same time that said dye composition is applied to said fibers, or sequentially with the dye composition.
According to this embodiment of the dyeing process of the invention, the above-described dyeing composition is preferably mixed at the time of use with an oxidizing composition comprising, in a medium suitable for dyeing, at least one oxidizing agent which is present in an amount sufficient for color development. The resulting mixture is subsequently applied to the keratinous fibers and left to act for approximately 3 to 50 minutes, preferably for approximately 5 to 30 minutes, after which the fibers are rinsed, optionally washed with shampoo, rinsed again and dried.
The oxidizing agent present in the oxidizing composition as defined above can be chosen from the oxidizing agents conventionally used for the oxidation dyeing of keratinous fibers, among which preferred oxidizing agents are: hydrogen peroxide, urea hydrogen peroxide, alkali metal bromates, persalts, such as perborates and persulphates, and enzymes, such as peroxidases and oxidoreductases with 2 unpaired electrons. It is particularly preferred to use hydrogen peroxide.
The pH of the oxidizing composition comprising the oxidizing agent as defined above is such that, after it has been mixed with the dyeing composition, the pH of the resulting composition, applied to the keratinous fibers, preferably ranges from approximately 3 to 12, and more preferably from 5 to 11. The pH can be adjusted to the desired value by means of acidifying or basifying agents which are commonly used in dyeing keratinous fibers and are as defined above.
The oxidizing composition as defined above can also contain various adjuvants which are conventionally employed in hair-dyeing compositions and are as defined above.
The composition which is ultimately applied to the keratinous fibers can be in various forms, such as in the form of liquids, creams or gels, or in any other form suitable for dyeing keratinous fibers, and in particular human hair.
Another aspect of the invention is a multi-compartment device or xe2x80x9ckitxe2x80x9d or any other multi-compartment packaging system, a first compartment of which contains the dyeing composition as defined above and a second compartment of which contains the oxidizing composition as defined above. These devices may be equipped with a means for delivering the desired mixture onto the hair, such as the devices described in Patent FR-2,586,913 the disclosure of which is specifically incorporated by reference herein.
Certain compounds of formula (I), which are used as an oxidation base within the scope of the invention are novel and, to that extent, are further provided by the invention.
These novel compounds of formula (Ixe2x80x2) and the acid addition salts thereof correspond to the following formulae (Ixe2x80x2a) to (Ixe2x80x2f): 
in which Rxe2x80x21, Rxe2x80x22, Rxe2x80x23 and Rxe2x80x24have the same meanings as those indicated above for R1, R2, R3 and R4 of formula (I); it being understood that:
in the compounds of formula (Ixe2x80x2b):
i) when Rxe2x80x21 represents a methyl radical and when Rxe2x80x22 represents a hydrogen atom, then Rxe2x80x23 is other than a methyl radical or than a (CH2)3xe2x80x94SO2xe2x80x94(CH2)15xe2x80x94CH3 or CH(CH3)xe2x80x94CH2xe2x80x94SO2xe2x80x94(CH2)11xe2x80x94CH3 radical;
ii) when Rxe2x80x21 represents a tert-butyl radical and when Rxe2x80x22 represents a hydrogen atom, then Rxe2x80x23 is other than a (CH2)3xe2x80x94SO2xe2x80x94(CH2)11xe2x80x94CH3 radical;
in the compounds of formula (Ixe2x80x2d):
when Rxe2x80x23 and Rxe2x80x24 together form a benzene radical and when Rxe2x80x22 represents a hydrogen atom, then Rxe2x80x21 is other than a methyl, xe2x80x94CONH2 or carboxyl radical;
when Rxe2x80x23 and Rxe2x80x24 together form a benzene radical substituted by a sulphonyl radical in the 4 position and when Rxe2x80x22 represents a hydrogen atom, then Rxe2x80x21 is other than a phenyl radical, a xe2x80x94(CH2)16xe2x80x94CH3 radical or a xe2x80x94COOH radical;
when Rxe2x80x23 and Rxe2x80x24 together form a benzene radical substituted by a carboxyl radical in the 4 position and when Rxe2x80x22 represents a hydrogen atom, then Rxe2x80x21 is other than a carboxyl radical.
The various compounds excluded by the above reservations are known in the photographic field or as analytical reagents (see in particular JP 02188748, JP 63074055, JP 61160745 and JP 60172982).
Preferred novel compounds of formula (Ixe2x80x2a) above, are:
7-amino-2-methylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-2-phenylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-methyl-2-ethylpyrazolo[1,5-b]-1,2,4triazole;
7-amino-6-methyl-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-methyl-2-phenylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-carboxy-2-methylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-carboxy-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-carboxy-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-carboxy-2-phenylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-phenyl-2-methylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-phenyl-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-phenyl-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;
6,7-diamino-2-methylpyrazolo[1,5-b]-1,2,4-triazole;
6,7-diamino-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;
6,7-diamino-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;
6,7-diamino-2-phenylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-ethylthio-2-methylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-ethylthio-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-ethylthio-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-ethylthio-2-phenylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-ethoxy-2-methylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-ethoxy-2-ethylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-ethoxy-2-isopropylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-ethoxy-2-phenylpyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-methyl-2-(2xe2x80x2-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-carboxy-2-(2xe2x80x2-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-phenyl-2-(2xe2x80x2-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-ethylthio-2-(2xe2x80x2-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;
7-amino-2-(2xe2x80x2-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;
7-amino-2-(2xe2x80x2-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-methyl-2-(2xe2x80x2-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-ethylthio-2-(2xe2x80x2-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-carboxy-2-(2 xe2x80x2-hydroxyethyl)pyrazolo[1,5-b-1,2,4-triazole;
7-amino-6-phenyl-2-(2xe2x80x2-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;
6,7-diamino-2-( 2xe2x80x2-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;
6,7-diamino-2-(2xe2x80x2-hydroxyethyl)pyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-ethoxy-2-(2xe2x80x2-aminoethyl)pyrazolo[1,5-b]-1,2,4-triazole;
7-amino-6-ethoxy-2-(2xe2x80x2-hydroxyethyl)pyrazolo[1,5-b-]1,2,4-triazole;
and the acid addition salts thereof.
Preferred novel compounds of formula (Ixe2x80x2b), are:
7-amino-3-methylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-3-(2xe2x80x2-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-3-(2xe2x80x2-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-methyl-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-3,6-dimethylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-methyl-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-methyl-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-methyl-3-(2xe2x80x2-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-methyl-3-(2xe2x80x2-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-methyl-3-(methylthio)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-phenyl-3-methylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-phenyl-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-phenyl-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-phenyl-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-phenyl-3-(2xe2x80x2-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-phenyl-3-(2xe2x80x2-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-phenyl-3-(methylthio)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-ethylthio-3-methylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-ethylthio-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-ethylthio-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-ethylthio-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-ethylthio-3-(2xe2x80x2-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-ethylthio-3-(2xe2x80x2-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-trifluoromethyl-3-(methylthio)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-(trifluoromethyl)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-carboxy-3-methylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-carboxy-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-carboxy-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-carboxy-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-carboxy-3-(2xe2x80x2-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-carboxy-3-(2xe2x80x2-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;
6,7-diamino-3-methylpyrazolo[3,2-c]-1,2,4-triazole;
6,7-diamino-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;
6,7-diamino-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;
6,7-diamino-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-ethoxy-3-methylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-ethoxy-3-ethylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-ethoxy-3-isopropylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-ethoxy-3-phenylpyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-ethoxy-3-(2xe2x80x2-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;
7-amino-6-ethoxy-3-(2xe2x80x2-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;
6,7-diamino-3-(2xe2x80x2-aminoethyl)pyrazolo[3,2-c]-1,2,4-triazole;
6,7-diamino-3-(2xe2x80x2-hydroxyethyl)pyrazolo[3,2-c]-1,2,4-triazole;
and the acid addition salts thereof.
Preferred novel compounds of formula (Ixe2x80x2c), are:
7-amino-6-methylpyrazolo[5,1-e]tetrazole;
7-amino-6-phenylpyrazolo[5,1-e]tetrazole;
7-amino-6-carboxypyrazolo[5,1-e]tetrazole;
and the acid addition salts thereof.
Preferred novel compounds of formula (Ixe2x80x2d), are:
7-aminopyrazolo[1,5-a]imidazole;
7-amino-2-methylpyrazolo[1,5-a]imidazole;
7-amino-2-phenylpyrazolo[1,5-a]imidazole;
7-aminopyrazolo[1,5-a]benzimidazole;
7-amino-6-methylpyrazolo[1,5-a]imidazole;
7-amino-2,6-dimethylpyrazolo[1,5-a]imidazole;
7-amino-6-methyl-2-phenylpyrazolo[1,5-a]imidazole;
7-amino-6-phenylpyrazolo[1,5-a]imidazole;
7-amino-6-phenyl-2-methylpyrazolo[1,5-a]imidazole;
7-amino-2,6-diphenylpyrazolo[1,5-a]imidazole;
7-amino-6-phenylpyrazolo[1,5-a]benzimidazole;
7-amino-6-carboxypyrazolo[1,5-a]imidazole;
7-amino-6-carboxy-2-methylpyrazolo[1,5-a]imidazole;
7-amino-6-carboxy-2-phenylpyrazolo[1,5-a]imidazole;
7-amino-6-ethoxypyrazolo[1,5-a]imidazole;
7-amino-6-ethoxy-2-methylpyrazolo[1,5-a]imidazole;
7-amino-6-ethoxy-2-phenylpyrazolo[1,5-a]imidazole;
7-amino-6-ethoxypyrazolo[1,5-a]benzimidazole;
7-amino-6-(trifluoromethyl)pyrazolo[1,5-a]benzimidazole;
7-amino-6-aminopyrazolo[1,5-a]imidazole;
7-amino-6-amino-2-methylpyrazolo[1,5-a]imidazole;
7-amino-6-amino-2-phenylpyrazolo[1,5-a]imidazole;
7-amino-6-aminopyrazolo[1,5-a]benzimidazole;
7-amino-6-(ethylthio)pyrazolo[1,5-a]imidazole;
7-amino-6-ethylthio-2-methylpyrazolo[1,5-a]imidazole;
7-amino-6-ethylthio-2-phenylpyrazolo[1,5-a]imidazole;
7-amino-6-methyl-2-hydroxypyrazolo[1,5-a]imidazole;
7-amino-6-phenyl-2-hydroxypyrazolo[1,5-a]imidazole;
7-amino-6-ethoxy-2-hydroxypyrazolo[1,5-a]imidazole;
7-amino-6-ethylthio-2-hydroxypyrazolo[1,5-a]imidazole;
6,7-diamino-2-hydroxypyrazolo[1,5-a]imidazole;
and the acid addition salts thereof.
Preferred novel compounds of formula (Ixe2x80x2e), are:
5,8-diamino-4-methylpyrazolo[5,1-e]pyrazole;
5,7,8-triamino-4-methylpyrazolo[5,1-e]pyrazole;
and the acid addition salts thereof.
Preferred novel compounds of formula (Ixe2x80x2f), are:
6-amino-5-methylpyrazolo[5,1-e]-1,2,3-triazole;
6-amino-5-phenylpyrazolo[5,1-e]-1,2,3-triazole;
and the acid addition salts thereof.
The novel compounds of formula (Ixe2x80x2) in accordance with the present invention can be prepared according to the methods described in the following patent applications and patents: FR 2,075,583, EP-A-119,860, EP-A-285,274, EP-A-244,160, EP-A-578,248, GB 1,458,377, U.S. Pat. Nos. 3,227,554, 3,419,391, 3,061,432, 4,500,630, 3,725,067, 3,926,631, 5,457,210, JP 84/99437, JP 83/42045, JP 84/162548, JP 84/171956, JP 85/33552, JP 85/43659, JP 85/172982, JP 85/190779, JP 41/33053, EP 433,854, JP 62/129851 JP 60/140241, as well as in the following publications:
Chem. Ber., 32, 797 (1899), Chem. Ber., 89, 2550 (1956),
J. Chem. Soc. Perkin Trans. I, 2047 (1977),
J. Prakt. Chem., 320, 533 (1978).
The following examples are intended to illustrate the invention, without, however, limiting its scope.